JP2001514649A - 4,4-Difluorobut-3-enylsulfinic acids and their use as pesticides - Google Patents

Abstract

(57) The present invention relates to a compound of the formula (I): CF ₂ ＣCX—CH ₂ —CH ₂ —S (O) —R, wherein X represents hydrogen, halogen or lower alkyl; Represents a group OR ¹ or NR ² R ³ , wherein R ¹ , R ² and R ³ are as defined herein. These compounds are useful for controlling agricultural pests such as insects.

Description

DETAILED DESCRIPTION OF THE INVENTION              4,4-difluorobut-3-enylsulfinic acid                 And their use as pesticides   The present invention relates to sulfur-containing acids and their derivatives, and more particularly to pest control. Useful as a pesticide, pestidal agent , Sulfur-containing acids and their salts, esters and amides.   In a first aspect, the present invention provides compounds of formula (I):         CF_Two= CX-CH_Two-CH_Two-S (O) -R (I) (Where   X represents hydrogen, halogen or lower alkyl;   R is a group OR¹Or NR^TwoR^ThreeWhere R¹, R^TwoAnd R^ThreeIs German Hydrogen and alkyl, alkenyl, alkynyl, cycloalkyl, ant Aralkyl, alkaryl, heteroaryl and heteroarylalkyl Or a group selected from R^TwoAnd R^ThreeIs a nitrogen-containing heterocycle with adjacent nitrogen atoms Represents a formula group, which further contains a heteroatom selected from oxygen, sulfur and nitrogen. May have R¹, R^TwoAnd R^ThreeAny of the groups represented by halogen, cyano, Toro, hydroxy, hydrocarbyloxy, amino, hydrocarbylamino, di Hydrocarbylamino, carboxy, hydrocarbyloxycarbonyl, carbo Xylamide, hydrocarbylaminocarbonyl, dihydrocarbylaminocarbo Nil, hydrocarbylthio, hydrocarbylsulfinyl and hydrocarbyl Optionally substituted with one or more substituents selected from sulfonyl. Wherein each of these hydrocarbyl groups is one or more of the foregoing. And a salt thereof.   Preferred compounds are those where X is hydrogen, fluorine or methyl.   R¹, R^TwoAnd R^ThreeIf any of represents a group containing a carbon atom, they are preferred. Containing up to 12 carbon atoms, aryl, aralkyl and alkaryl Except for radicals, more preferably it contains up to 6 carbon atoms.   Nitrogen containing which may further contain a heteroatom selected from oxygen, sulfur and nitrogen Formula NR representing a heterocyclic group^TwoR^ThreeExamples of groups are, for example, piperidine, piperazine , Morpholine, thiazolidine, imidazoline and the like.   R¹Is hydroxy or R¹, R^TwoAnd R^ThreeRepresents a group containing acidic hydrogen In this case, the salts of the compound of formula (I) are, for example, sodium, potassium, calcium Metal salts, including ammonium, magnesium, copper, zinc or iron, or ammonium salts , An amine salt or a quaternary ammonium salt.   Specific examples of compounds according to the present invention include those shown in Tables I and IA below. It is.   Compounds of formula (I) can be prepared as follows. For convenience, the base CF_Two= CX-CH_Two− CH_Two-Is represented by Q in the following description.   Compounds in which R represents hydroxy are sulfinic acids, for example the corresponding formula Q- SO_TwoReducing the sulfonyl chloride of Cl or the corresponding benzothiazole- 2-yl sulfone was prepared according to Chem. Lett. 2125 (1984) It can be produced via a sodium salt by reduction. Other manufacturing methods , A Grignard reagent of formula Q-Mg-Cl and sulfur dioxide are described in Chem. Revs.4 8 , 69 (1950).   R is OR¹Is a compound represented by, for example, Synthesis, p. . 441 (1978) by mild esterification. Or by treating those acids with thionyl chloride or oxalyl chloride. Via the sulfinyl chloride prepared¹By reacting with OH alcohol Can be manufactured. Another method involves synthesizing a disulfide of the formula QSSQ with Synthesi s, p. 252 (1988) in the presence of alcohols. By treating with a compound. In yet another method, the formula Q-SO_TwoC l of the sulfonyl chloride in J.I. Org. Chem.52, 2598 (1987) Under reduced conditions as described above, for example in the presence of trimethyl phosphinate, the alcohol Process with tools.   R is NR^TwoR^ThreeIs a sulfinyl chloride of the formula QS (O) Cl HR^TwoR^ThreeBy reacting the compound with   Sulfinyl chlorides (and) useful for the preparation of the compounds of formula (I) described herein And other halides) are new compounds. In another embodiment, the present invention provides a compound of formula (I) Compounds of formula (II) useful as intermediates in the preparation of compounds of formula         CF_Two= CX-CH_Two-CH_Two-S (O) -Y (II) Wherein X is hydrogen or halogen or lower alkyl, preferably hydrogen or fluor. And Y is halogen, preferably chlorine). Of the formula (II) Specific examples of the compound include 1- (4,4-difluorobut-3-ene) sulfinyl Chloride and 1- (4,4,4-trifluorobut-3-ene) sulfinyl Includes chloride.   Detailed information on the preparation of individual compounds can be found in the Examples below.   In still another aspect, the present invention provides a method for locating pests such as insects in a locus. s) The method of controlling pests in which A pesticidal composition comprising a compound of formula I or an acid addition salt thereof in an amount effective to combat pesticides. By providing a method.   Compounds of formula I and acid addition salts thereof are useful in insect pests such as Lepidoptera, Diptera, Coleoptera and Coleoptera (Diabrotica, root) Insects (including worms), as well as other invertebrate pests, such as pests of the order Acarina Can be used to disinfect and control intrusion. Controlled by using the compound of the present invention Agriculture (this term refers to food and fiber production) (Including growing crops for commercial use), horticulture and livestock, forestry, and plant-based products Pests associated with the storage of (eg, fruits, cereals and wood), and human and And pests associated with transmission of animal diseases. Inhibited by compounds of formula I Examples of possible harmful species of insects and mites include: Miss Persike (Myzus persicae) (Aphid), Affi Su GossipAphis gossipii) (Aphid), Affith Fa Be (Aphis Fabae) (Aphid), Edes Ijipuchi (Aedes a egypti ) (Mosquito), Anopheles (Anopheles) Seed (mosquito), Kyu Rex genus (Culex) Species (mosquito), Disdelcas faciatus (Dysde rcus fasciatus ) (Mekurakamemushi), Musca Domestika (M usca domestica ) (Housefly), Piris Brassique (Pier is brassicae ) (White Butterfly), Plutera Xylostella (Plutella xylostella) (Conaga), Fedon Cochlear Rie (Phaedon cochleariae) (Mustard beetle (ham A), Aonidiera (Aonidiella) Seeds (scale insects), thoria Roylodes (Trialeurodes) Seeds (whiteflies), Bemisia ta Basi (Bemisia tabaci) (Whiteflies), Braterra germanica (Blattella germanica) (Cockroach), periplaneta a Merikana (Periplaneta americana) (Cockroach), bra Tta orientalis (Blatta orientalis)(cockroach), Spodoptera litoralis (Spodoptera littoralis) (W Tayoto), Heliodis Villecens (Heliothis villages cens ) (Yaga), Cortisetes Terminifera (Shortet es terminera ) (Grasshopper), Diabrotica species (rootwort) Agrotis)Agrotis) Species (Pyraminidae), Cairo Parters (Chilo partellulus) (Nikameiga), Nila Parvata Luge (Nilaparvata lugens) (Funka), nefothetic Su Synchiceps (Nephotettix cincticeps)(side Bai), Panonikas Urumi (Panonychus ulmi) (Apple Nada) D) Panonikas Sitli (Panonychus citri) (Mikanhada D), Tetranikas Ultica (Tetranychus urticae) ( Ticks), Tetranikas cinnabalinus (Tetranychus ci nnabarinus ) (Pycium mites), Filkoptorta Olaybora (Phylcoptruta oleivora ) (Rutaceae), Polyph Agotarsonemus ratas (Polyphagotarsonemus lat us ) (Dermatophagoid mites) and Brevipalpas (Brevipalpus ) Species (mites).   Compounds of formula I in the presence of harmful nematodes, insects or mites, or harmful For application to plants susceptible to insects, insects or mites, the The light compound can be a compound of formula I as well as a suitable inert diluent or carrier material and And / or a composition containing a surfactant. For control of harmful nematodes Generally, the amount of the composition applied is 0.01 to 10 kg / ha of the active ingredient, preferably Or 0.1 to 6 kg / ha.   Apply these compositions to soil, plants or seeds, pests, Spray powder, wettable powder, granule (slow release or immediate release) ), Concentrated emulsion or concentrated suspension, liquid, emulsion, seed dressing, fume / Smoke formulations or controlled release compositions such as microencapsulated granules Or it can be applied in the form of a suspension.   Spray powders contain the active ingredient in one or more finely divided solid carriers and And / or diluents such as natural clay, kaolin, pyrophyllite, ben Tonite, alumina, montmorillonite, diatomaceous earth (kieselguhr, Diatomaceous earth), chalk, calcium phosphate, calcium carbonate Calcium and magnesium carbonate, sulfur, lime, flour, talc, and other And by mixing with an organic solid carrier.   Granules include porous granular materials such as pumice, attapulgite clay, -Soil, diatomaceous earth, ground corn cob, etc., or hard core material, For example, the active ingredient is absorbed into sand, silicates, mineral carbonates, sulfates, phosphonates, etc. It is prepared by allowing Impregnation, binding or binding of the solid carrier with the active ingredient Materials commonly used to assist coatings include aliphatic and aromatic petroleum solvents, Alcohol, polyvinyl acetate, polyvinyl alcohol, ethers, ketones, Includes esters, dextrins, sugars and vegetable oils.   Other control of microencapsulated compound (microcapsule suspension, CS) Release formulations can also be used, especially for extended release and seed treatment over extended periods of time.   Alternatively, the composition may be a liquid for use as a dip, irrigation additive or spray. It may be in the form of a body preparation, which generally comprises one or more known moisturizing agents. Aqueous dispersions or emulsions in the presence of dispersants, dispersants or emulsifiers (surfactants) is there. Compositions for use in aqueous dispersions or emulsions generally contain a high proportion of Emulsifiable concentrates (EC) or concentrates containing one or more active ingredients Supplied in suspension (SC) form. EC is usually converted into a substantially non-volatile organic solvent. A homogeneous liquid composition containing the dissolved active ingredient. SC stands for It is a dispersion of solid active ingredient of fine particle size. To apply the concentrates, It is diluted in water and applied to the area to be treated, usually by spraying.   Liquid solvents suitable for EC include methyl ketone, methyl isobutyl ketone, Hexanone, xylene, toluene, chlorobenzene, paraffin, kerosene, e Wight oil, alcohols (eg butanol), methyl naphthalene, trimethyi Benzene, trichloroethylene, N-methyl-2-pyrrolidone and Drofurfuryl alcohol (THFA) is included.   Wetting, dispersing and emulsifying agents can be cationic, anionic or nonionic. Any of them may be used. Suitable substances of the cationic type include, for example, quaternary ammonia. Compounds, such as cetyltrimethylammonium bromide. Anion Suitable substances of the type include, for example, soaps, salts of aliphatic monoesters of sulfuric acid, and the like. For example, sodium lauryl sulfate, salts of sulfonated aromatic compounds such as dode Sodium silbenzenesulfonate, sodium lignosulfonate, -calcium Or ammonium or butyl naphthalenesulfonate; Sodium salt mixture of isopropyl and triisopropylnaphthalenesulfonic acid Things are included. Suitable non-ionic substances include, for example, ethylene oxide and fats. Alcohol (eg oleyl or cetyl alcohol) or alcohol Kill phenols (eg octyl phenol, nonyl phenol and octyl phenol) Condensate with lucresol). Other non-ionic substances are compatible with long chain fatty acids. Partial esters derived from water hexitol, these partial esters and ethylene Oxide condensates, as well as lecithin.   Concentrates can withstand prolonged storage, and after such storage have been diluted with water and sprayed with conventional spray equipment. To form an aqueous preparation that is maintained homogeneous for a period sufficient to allow them to be applied in a device Is often required. The concentrated solution comprises one or more active ingredients 10 ８５85% by weight. When diluted to form an aqueous preparation, These preparations may contain varying amounts of the active ingredient depending on the purpose for which they are used. Can be.   Compounds of formula I are treated with a powder for seed treatment (dry seed treatment agent DS or water-dispersible Powder WS) or liquid (fluid concentrated liquid FS, liquid seed treating agent LS, microcapsule) Pseel suspension (CS)).   When used, receive pests, pests, or pests. Any known method for applying a harmful-control composition to a growing plant The composition in any manner, for example by spraying, spraying, or granulating. be able to.   The compounds of the formula I may be the only components of the composition or, if appropriate, Or more other active ingredients such as insecticides, synergists, herbicides, fungicides Alternatively, it may be mixed with a plant growth regulator. Mixed with the compound of formula I Additional active ingredients suitable for are compounds that extend the spectrum of activity of the compositions of the present invention, Or a compound that enhances the persistence of the composition at the location of the pest. No. They may act synergistically with the activity of the compounds of the formula I, or The activity may be supplemented by increasing the degree or overcoming the repellency. This Multi-component mixtures further overcome or prevent the development of resistance to each component Will help you. Specific examples of additional active ingredients to include may be It will depend on the application and the type of supplementary action required. Examples of suitable pesticides Includes:   a) Pyrethroids such as permethrin, S Fenvalerate, deltamethrin (delta) methrin), cyhalothrin, especially lambda Halothrin, bifenthrin, fenpropatrin (Fenpropathrin), cyfluthrin, te Tefluthrin, fish-safe pyrethroids, such as Tofenprox, natural pyrethrin, tetrameth Phosphorus (tetralmethrin), s-bioalletrin (bioalllet) hrin), fenfluthrin, praletrin (p ralletrin), and 5-benzyl-3-furylmethyl- (E)-( 1R, 3S) -2,2-dimethyl-3- (2-oxothiolan-3-ylideneme Tyl) cyclopropanecarboxylate;   b) organic phosphates, such as profenfos, Sulprofos, methyl parathion, azinphos-methyl (Azinphos-methyl), demeton-s-methyl (demetho) ns-methyl), heptenophos, thiomethoate (Thiometon), fenamiphos (monochrome), monochrome Monocrotophos, profenophos os), triazophos, methamidophos (methamphos) idophos), dimethoate, phosphamidon ( phosphamidon, malathion, chloropyri Phosphorylifos, Phosalon, Tel Terbufos, fensulfothion ion), phonophos, holate, horate Phoxim, pyrimiphos-methyl hyl), pirimiphos-ethyl, fenitrothion ) Or diazinon;   c) carbamates (including aryl carbamates), such as pirimicarb (Pirimicarb), cloetocarb, car Carbofuran, furatiociocar b), ethiophencarb, aldicarb (al dicarb), thiofurox, carbosurfan ( carbosulfan, bendiocarb, pheno Fenobucarb, propoxur or Oxamyl;   d) Benzoyl ureas, such as triflumuron Or chlorfluazuron;   e) Organotin compounds such as cyhexatin, phen Butatin oxide (fenbutatin oxide), azocyclotin (a zoclotin);   f) macrolides, such as avermectins, Or milbemycins, such as abamectin (ab amectin), ivermectin, and milbema Isin;   g) hormones and pheromones;   h) Organochlorine compounds such as benzene hexachloride, DDT, chlorda Chlordan or dierdrin;   i) amidines, such as chlordimeform ) Or amitraz;   j) smoking agents;   k) imidacloprid.   In addition to the main groups of insecticides listed above, specific targets may be identified where appropriate for the intended use of the mixture. Other pesticides can be used in the mixture. For example, pesticides that are selective for certain crops , For example, cartap or buprofezin Zin) and other rice pesticides (stemborer) specific pesticides for rice it can. Alternatively, pesticides specific to a particular insect species / stage, such as clofente Gin (chlofentezine), flubenzimine (flubenzimi) ne), hexithiazox and tetradiphone Egg-larvae control agents such as (tetradifon), dicofo l) or motifs such as propargite (mot) ilicide), bromopropylate, Acaricide, such as chlorobenzilate, or Hydramethylron, cyromazine (cyrom) azine), methoprene, chlorofluazuron (c chlorofluazuron) and diflubenzuron (diflubenz) (Uron) can also be included in the compositions of the present invention.   Examples of suitable synergists for use in the compositions of the present invention include piperonyl butoxide, Sesamax, safloxan and de Includes decyl imidazole. Herbicides, fungicides suitable for inclusion in the composition Drugs and plant growth regulators will depend on the intended target and the required action. Would. An example of a rice selective herbicide that can be included is propanil (prop) anil) and an example of a plant growth regulator suitable for use in cotton is "Pix ( P ix) "and examples of fungicides suitable for use in rice include blasticide (b lastostides), for example, bustycidin-S (blasticidi) nS). The ratio of the compound of formula I to the other active ingredients in the composition is It will depend on many factors, such as the type of target, the effect required on the mixture. I However, in general, the active ingredient added to the composition will be approximately in the proportion in which it is usually used, or Or if synergy occurs, will be applied at a slightly lower rate .   The invention is illustrated by the following example. Examples 1 to 3 include compounds of formula (I) The production of is shown. Examples 4-11 include pest control suitable for application of compounds of formula I 1 shows a composition for use. The following components are called under their registered trademarks and have the following composition:Registered trademark composition Synperonic NP8} Nonylphenol-ethylene oxide condensate (Symperonic NP8) Symperonic NP13} Symperonic OP10} Aromasol H Alkylbenzene solvent (Aromasol H) SolveEsso 200 inert diluent (Solvesso 200) Celtorol polysaccharide (Keltrol)                                 Example 1   This indicates the preparation of bis (4,4-difluorobut-3-enyl) disulfide. You.Step 1 :Production of 1,4-dibromo-1,1,2-trifluorobutane   4-bromo-1,1,2-trifluorobut-1-ene (Fluorochem) ( 240 g) before use with water (300 cm^Three), Then brine (300 cm^Three)so Washed and dried (MgSO_Four). Benzoyl peroxide (about 0.7g) at a time Hydrogen bromide gas to the mixture at a rate to maintain the reaction temperature between 30 and 40 ° C. I got into it. After 2 hours, the GC of the reaction mixture sample shows little starting material remaining This Was shown. The reaction mixture was washed with water (300 cm^Three), Then saturated sodium bicarbonate Solution and then water again (300 cm^Three), Dried (MgSO 4)_Four), Filtered A pale yellow oil was obtained (296.7 g). This is 1,4-dibromo-1,1,2- It was identified as trifluorobutane. This substance exceeds 98% purity by GC analysis Rukoto has been shown. Step 2:Production of 4-bromo-1,1-difluorobut-1-ene   Acetone (6 cm) containing water (1 drop)^Three1,)-Dibromo-1 in To a stirred solution of 1,1,2-trifluorobutane (1.38 g) under a nitrogen atmosphere. Lead dust (0.88 g) was added. After 45 minutes, GC analysis shows that most of the starting material has been consumed It was shown. This mixture is then mixed with acetone in acetone containing traces of water. It was further added to lead dust (3 g) (preheated to 55 ° C.). After another 20 minutes at this temperature, GC analysis indicated that all of the starting material had been consumed. This is a debromination fluorine reaction Indicates that has started. Then, while maintaining the reaction mixture at 55 ° C., The starting material (12.34 g) was added to the reaction mixture over 75 minutes. Then 9 more Heating was continued for 5 minutes. GC analysis of the sample showed that about 3% of the starting dibromo compound was unchanged It has been shown to remain. Further, zinc dust (0.16 g) was added, and the starting material was Heating was continued until GC indicated that all had been consumed. Residual zinc in acetone solution Decanted from 4-bromo-1,1-diene suitable for use in subsequent chemical reactions. A fluorobut-1-ene solution was obtained.Step 3 :Preparation of bis (4,4-difluorobut-2-enyl) disulfide   Sodium disulfide solution (Ethanol (250cm^Three) In sodium sulfide 9-hydrate (prepared from 53 g) and sulfur (7.0 g) was converted to ethanol (10 g). 0cm^Three)) To 1-bromo-4,4-difluorobut-3-ene (50 g). Added. The mixture is gradually heated and stirred under reflux for 2 hours, then cooled and reduced. Evaporate under pressure. The residue was extracted with diethyl ether, the organic phase was filtered and brominated. The sodium was removed and the ether was evaporated under reduced pressure to give a liquid. this Distillation was performed at 16 mmHg and a boiling point of 120 ° C. to obtain bis (4,4-difluorobut-3-yne). (Enyl) disulfide (24 g) was obtained as a colorless liquid.                                 Example 2   This example illustrates n-hexyl 4,4-difluorobut-3-enylsulfinate The production of is shown.   n-hexanol (10 cm^Three) In the bis (4,4-difluorobut-3-e) Nyl) disulfide (1.0 g) with potassium carbonate (anhydrous, 0.54 g) Stir under a nitrogen atmosphere and cool to 0 ° C. N-bromosuccinimide was added to this mixture. (2.0 g) was added and the reaction was allowed to warm to ambient temperature over 1.5 hours. Reactant To diethyl ether (150 cm^Three) Extracted into water (100cm^ThreeWash twice) Clean, dry (magnesium sulfate) and remove the solvent by evaporation under reduced pressure. The resulting oil was evaporated under reduced pressure (110 ° C. at 15 mm Hg) to give n- Remove xanol and chromatograph residual oil (silica, dichloromethane) To give the desired product as a pale yellow-orange oil (0.14 g). Chemical ionization mass spectrum MNH_Four+ Molecular ion 258.                                 Example 3   This example demonstrates the use of 4,4-difluorobut-3-enylsulfinic acid (sodium 2 shows the production of the salt).Step 1   Dichloromethane (15cm^Three2-), 4- (4,4-difluorobut-3-enyl) Ruthio) benzothiazole (produced as described in British Patent Application No. 2270689A). 8.25 g) in water (25 cm^ThreePeroxyphthalic acid in magnesia) Mixture of sodium hexahydrate (25.7 g, 70-80%, industrial) ). The mixture was stirred for 2 days, diluted with dichloromethane and water, The organic phase was separated, washed with aqueous sodium carbonate solution, water and dried (magnesium sulfate). Cium). The solvent was evaporated under reduced pressure to give 2- (4,4-difluorobut-3-e. Nylsulfonyl) benzothiazole was obtained as a colorless oil (4.9 g).Step 2   Methanol (13cm^Three2-)-(4,4-difluorobut-3-enyls) (Ronyl) benzothiazole (1.9 g) was stirred at ambient temperature to give sodium borohydride. Thorium (0.52 g) was treated in small portions. The reaction mixture is stirred for 2 hours and Was added to sodium borohydride (0.50 g) and stored at ambient temperature for 18 hours. Was. The solution was evaporated under reduced pressure and the residue was partitioned between water and diethyl ether. Was. The aqueous phase was separated and diethyl ether (150 cm^Three2 times) and re-extract The zothiazole is removed and the aqueous phase is evaporated under reduced pressure to give the desired product as a hygroscopic solid. I got it.                                 Example 4   This example demonstrates N-4-chlorobenzyl 4,4-difluorobut-3-enyls 2 shows the production of rufinamide.Step 1 Production of 4,4-difluorobut-3-enylsulfinyl chloride   Thionyl chloride (200 ml) in n-hexane (400 ml) was stirred at ambient temperature. After stirring, 4,4-difluorobut-3-enylsulfinic acid sodium salt (44 g) ) Was added in small portions. After the addition is complete, heat the reaction mixture to reflux for 4.5 hours under nitrogen. And cooled to ambient temperature and then filtered. The filtrate is evaporated under reduced pressure to give a liquid. Was done. This was distilled and a fraction having a pressure of 0.1 mmHg and a boiling point of 50 to 60 ° C. was collected. 4,4-Difluorobut-3-enylsulfinyl chloride (5.6 g) was obtained. . IR (thin film) n: 2946,1725,1380,1150,730cm^-1.Step 2   4,4-Difluorobut-3-enyl in dry diethyl ether (1.5 ml) Rusulfinyl chloride (0.5 g) was stirred at ambient temperature and stirred with diethyl ether ( 4-Chlorobenzylamine (1.0 g) in 1.5 ml) was added dropwise. The mixture Stored at ambient temperature for 2 days, then added water (100 ml). HCl mixture Acidify with solution (2M) and extract with dichloromethane (100ml). Organic fraction Was separated, washed with water, and then dried over anhydrous magnesium sulfate. Decompress the solvent Under Evaporation gave an oil. This was chromatographed (silica; ethyl acetate / (Hexane 2: 1, volume ratio). Lurobut-3-enylsulfinamide (0.094 g) as an off-white solid Obtained. 37-8 ° C.                                 Example 5   This example can be easily converted to a liquid preparation diluted with water and suitable for spraying. 1 shows an emulsifiable concentrate composition. This concentrate has the following composition:                                           weight% Compound No. 1 25.5 Symperonic NP13 2.5 Calcium dodecylbenzenesulfonate 2.5 Aromasol H 70                                 Example 6   This example can be easily converted to a liquid preparation diluted with water and suitable for spraying. 1 shows a wettable powder composition. This wettable powder has the following composition:                                           weight% Compound No. 13 25.0 Silica 25.0 Sodium lignosulfonate 5.0 Sodium lauryl sulfate 2.0 Kaolinite 43.0                                 Example 7   This example shows a dusting powder that can be applied as it is to plants or other surfaces. This This is 1% by weight of Compound No. It contains 25 and 99% by weight of talc.                                 Example 8   This example is for mixing with a paraffinic diluent and then applying the ultra-low volume method. Figure 3 shows a suitable concentrate formulation.                                           weight% Compound No. 19 90.0 SolveEsso 200 10.0                                 Example 9   This example illustrates a formulation suitable for dilution with water and application as an aqueous propellant. 3 shows a concentrated capsule suspension that can be easily converted.                                                     weight% Compound No. 4 10.0 Alkylbenzene-based solvent (eg, Aromasol H) 5.0 Toluene diisocyanate 3.0 Ethylenediamine 2.0 Polyvinyl alcohol 2.0 Bentonite 1.5 Polysaccharides (eg Celtrol) 0.1 Water 76.4                                Example 10   Granular formulation that can be applied as is:                                           weight% Compound No. 1 0.5 SolveEsso 200 0.2 Nonylphenol ethoxylate 0.1 (For example, Symperonic NP8) Calcium carbonate granules 99.2 (0.3-0.7mm)                                Example 11   Concentrated aqueous suspension:                                           weight% Compound No. 21 5.0 Kaolinite 15.0 Sodium lignosulfonate 3.0 Nonylphenol ethoxylate 1.5 (For example, Symperonic NP8) Propylene glycol 10.0 Bentonite 2.0 Polysaccharides (eg Celtrol) 0.1 Fungicides (eg Proxel 0.1   Proxel is a registered trademark) Water 63.3                                Example 12   This example shows a water-dispersible granular formulation.                                           weight% Compound No. 3 5 Silica 5 Sodium lignosulfonate 10 Sodium dioctyl sulfosuccinate 5 Sodium acetate 10 Montmorillonite powder 65                                Example 13   This example demonstrates the insecticidal properties of the compounds of formula I. Formulation using various pests The activity of the compound was measured. Unless otherwise noted, contains 500 ppm (by weight) of compound. The pest was treated with the liquid composition having. The composition was acetone and ethanol (5 0:50), the compound of the present invention was dissolved in a mixture of Wetting agent marketed under the trade name "Symperonic" NP8 until it contains the compound It was prepared by dilution with water containing 0.05% by weight. “Simperoni ッ Is a registered trademark.   The test method adopted for each pest is basically the same, Supported by a medium (usually a support, host plant, or food eaten by the pest) Treating the body and / or pest with the composition. Was. The pest mortality is then assessed at various times, usually 2-5 days after treatment. Was.   The results of the test on the peach beetle (Mothers persique) are shown below. This These results indicate the mortality grade (score) expressed as A, B or C. C is lethality 4 Less than 0%, B represents 40-79% mortality, A represents 80-100% mortality. This trial Infected Chinese cabbage leaves with aphids The infected composition was sprayed with the test composition, and the mortality was evaluated 3 days later.   In this test, Compound No. 1 and 3 gave grade A. In similar tests, these compounds The material was given a grade A against spider mites (Tetranikas urtica). Compound No. 2 1 gave Grade B to Heliodis villeces larvae. Compound 1 , 3 and 21 were nematode (meloidozin in) when applied at 12.5 ppm. Cognita,Meloidogyne incognita) Is given a grade A Was.

────────────────────────────────────────────────── ─── Continuation of front page    (81) Designated countries EP (AT, BE, CH, DE, DK, ES, FI, FR, GB, GR, IE, IT, L U, MC, NL, PT, SE), OA (BF, BJ, CF) , CG, CI, CM, GA, GN, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, M W, SD, SZ, UG, ZW), EA (AM, AZ, BY) , KG, KZ, MD, RU, TJ, TM), AL, AM , AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CU, CZ, DE, DK, EE, E S, FI, GB, GE, GH, GM, GW, HU, ID , IL, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, M G, MK, MN, MW, MX, NO, NZ, PL, PT , RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, US, UZ, V N, YU, ZW

Claims (1)

[Claims] 1. Compounds of formula (I): CF ₂ ＣCX—CH ₂ —CH ₂ —S (O) —R (I) wherein X represents hydrogen, halogen or lower alkyl, and R represents a group OR ¹ or NR ² R ³ , wherein R ¹ , R ² and R ³ are each independently selected from hydrogen and alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, alkaryl, heteroaryl and heteroarylalkyl groups. Luke, or R ² and R ³ represents a nitrogen-containing heterocyclic group together with the adjacent nitrogen atom, they oxygen may further contain heteroatoms selected from oxygen, sulfur and nitrogen, R ^1, R any group which is ² and R ³ represents halogen, cyano, nitro, hydroxy, hydrocarbyloxy, amino, hydrocarbylamino, dihydrocarbylamino, carboxy, human Optionally substituted with one or more substituents selected from locarbyloxycarbonyl, carboxamide, hydrocarbylaminocarbonyl, dihydrocarbylaminocarbonyl, hydrocarbylthio, hydrocarbylsulfinyl and hydrocarbylsulfonyl, wherein Any of the hydrocarbyl groups may be optionally substituted with one or more of the above substituents), and salts thereof. 2. The compound of formula (I) according to claim 1, wherein X is hydrogen, fluorine or methyl. 3. The compound of the formula (I) according to claim 1, wherein the compound is a compound wherein X is hydrogen or fluorine and R ¹ is hydrogen, and salts thereof. 4. The compound of claim 1, wherein the compound is selected from 4,4-difluorobut-3-enylsulfinic acid, and salts, esters and amides thereof. 5. 4,4-Difluorobut-3-enylsulfinic acid. 6. N-4-chlorobenzyl 4,4-difluoro-3-butenylsulfinamide. 7. Compounds of formula (II): wherein X is hydrogen or halogen or lower alkyl and Y is halogen. 8. The compound of claim 7, wherein X is hydrogen and Y is chlorine. 9. A pest control composition comprising a pest control effective amount of the compound of claim 1 and an agriculturally acceptable liquid or solid diluent. 10. A method of controlling pests at their location, comprising applying to the location a pest-controlling effective amount of the composition of claim 9. 11. 11. The method according to claim 10, wherein the pest is an insect, mite or nematode harmful to growing plants and the composition is applied to those plants or to the soil in which the plants are growing. 12. A method for controlling plant harmful nematodes that inhabits the soil, comprising treating the soil such that a nematode-suppressing amount of the compound according to claim 5 or a salt thereof is supplied into the soil.